Recent Advances in Co-Based Electrocatalysts for Hydrogen Evolution Reaction.

Water splitting is a promising technique in the sustainable "green hydrogen" generation to meet energy demands of modern society. Its industrial application is heavily dependent on the development of novel catalysts with high performance and low cost for hydrogen evolution reaction (HER). As a typical non-precious metal, cobalt-based catalysts have gained tremendous attention in recent years and shown a great prospect of commercialization. However, the complexity of the composition and structure of newly-developed Co-based catalysts make it urgent to comprehensively retrospect and summarize their advance and design strategies. Hence, in this review, the reaction mechanism of HER is first introduced and the possible role of the Co component during electrocatalysis is discussed. Then, various design strategies that could effectively enhance the intrinsic activity are summarized, including surface vacancy engineering, heteroatom doping, phase engineering, facet regulation, heterostructure construction, and the support effect. The recent progress of the advanced Co-based HER electrocatalysts is discussed, emphasizing that the application of the above design strategies can significantly improve performance by regulating the electronic structure and optimizing the binding energy to the crucial intermediates. At last, the prospects and challenges of Co-based catalysts are shown according to the viewpoint from fundamental explorations to industrial applications.